1. Field of the Invention
The present invention generally relates to removing organic contaminants from semiconductor electrolyte solutions.
2. Description of the Related Art
Metallization for sub-quarter micron sized features is a foundational technology for present and future generations of integrated circuit manufacturing processes. More particularly, in devices such as ultra large scale integration-type devices, i.e., devices having integrated circuits with more than a million logic gates, the multilevel interconnects that lie at the heart of these devices are generally formed by filling high aspect ratio interconnect features with a conductive material, such as copper or aluminum. Conventionally, deposition techniques such as chemical vapor deposition (CVD) and physical vapor deposition (PVD) have been used to fill these interconnect features. However, as interconnect sizes decrease and aspect ratios increase, void-free interconnect feature fill via conventional metallization techniques becomes increasingly difficult. As a result thereof, plating techniques, such as electrochemical plating (ECP) and electroless plating, for example, have emerged as viable processes for filling sub-quarter micron sized high aspect ratio interconnect features in integrated circuit manufacturing processes.
In an ECP process sub-quarter micron sized high aspect ratio features formed on a substrate surface may be efficiently filled with a conductive material, such as copper, for example. ECP plating processes are generally two stage processes, wherein a seed layer is first formed over the surface features of the substrate, and then the surface features of the substrate are exposed to an electrolyte solution, while an electrical bias is simultaneously applied between the substrate and an anode positioned within the electrolyte solution. The electrolyte solution is generally rich in ions to be plated onto the surface of the substrate, and therefore, the application of the electrical bias causes these ions to be urged out of the electrolyte solution and to be plated as a metal on the seed layer. The plated metal, which may be copper, for example, grows in thickness and forms a copper layer over the seed layer that operates to fill the features formed on the substrate surface.
In order to facilitate and control this plating process, several additives may be utilized in the electrolyte plating solution. For example, a typical electrolyte solution used for copper electroplating may consist of copper sulfate solution, which provides the copper to be plated, having sulfuric acid and copper chloride added thereto. The sulfuric acid may generally operate to modify the acidity and conductivity of the solution. The electrolytic solutions also generally contain various organic molecules, which may be accelerators, suppressors, levelers, brighteners, etc. These organic molecules are generally added to the plating solution in order to facilitate void-free super-fill of high aspect ratio features and planarized copper deposition. Accelerators, for example, may be sulfide-based molecules that locally accelerate electrical current at a given voltage where they absorb. Suppressors may be polymers of polyethylene glycol, mixtures of ethylene oxides and propylene oxides, or block copolymers of ethylene oxides and propylene oxides, for example, which tend to reduce electrical current at the sites where they absorb (the upper edges/corners of high aspect ratio features), and therefore, slow the plating process at those locations, which reduces premature closure of the feature before the feature is completely filled. Levelers, for example, may be nitrogen containing long chain polymers, which operate to facilitate planar plating. Additionally, the plating bath usually contains a small amount of chloride, generally between about 20 and about 60 ppm, which provides negative ions needed for adsorption of suppressor molecules on the cathode, while also facilitating proper anode corrosion.
Although the various organic additives facilitate the plating process and offer a control element over the interconnect formation processes, they also present a challenge, as the additives are known to eventually break down and become contaminate material in the electrolyte solution. Conventional plating apparatuses have traditionally dealt with these organic contaminants via bleed and feed methods (periodically replacing a portion of the electrolyte), extraction methods (filtering the electrolyte with a charcoal filter), photochemical decomposition methods (using UV in conjunction with ion exchange and acid-resistant filters), and/or ozone treatments (dispensing ozone into the electrolyte). However, these conventional methods are known to be inefficient, expensive to implement and operate, bulky, and/or to generate hazardous materials or other kinds of contaminants as byproducts. Therefore, there is a need for a method and apparatus for removing contaminants from semiconductor electroplating baths, wherein the method and apparatus addresses the deficiencies of conventional devices.